Novel Whitening Agents For Cellulosic Substrates

ABSTRACT

This invention relates to novel whitening agents for cellulosic substrates. The whitening agents are comprised of at least two components: at least one chromophore component and at least one polymeric component. Suitable chromophore components generally fluoresce blue, red, violet, or purple color when exposed to ultraviolet light, or they may absorb light to reflect these same shades. The whitening agents are further characterized by having a dispersion component value of the Hansen Solubility Parameter of less than or equal to about 17 MPa 0.5 . This invention also relates to laundry care compositions including but not limited to liquid and/or powder laundry detergent formulations and rinse added fabric softening (RAFS) compositions that comprise such whitening agents.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and is a divisional of co-pendingU.S. patent application Ser. No. 12/577,761 filed on Oct. 13, 2009,which claims priority to and is a divisional of U.S. Pat. No. 7,642,282issued on Jan. 5, 2010, both of which are hereby entirely incorporatedby reference.

TECHNICAL FIELD

This invention relates to novel whitening agents for cellulosicsubstrates. The whitening agents are comprised of at least twocomponents: at least one chromophore component and at least onepolymeric component. Suitable chromophore components generally fluoresceblue, red, violet, or purple color when exposed to ultraviolet light, orthey may absorb light to reflect these same shades. The whitening agentsare further characterized by having a dispersion component value of theHansen Solubility Parameter of less than or equal to about 17 MPa^(0.5).These whitening agents may be ideal for use in laundry care compositionsincluding but not limited to liquid and/or powder laundry detergentformulations and rinse added fabric softening (RAFS) compositions.

BACKGROUND

The use of whitening agents, either optical brighteners or blueingagents, in textile applications is well known in the prior art. Astextile substrates age, their color tends to fade or yellow due toexposure to light, air, soil, and natural degradation of the fibers thatcomprise the substrates. Thus, the purpose of whitening agents isgenerally to visually brighten these textile substrates and counteractthe fading and yellowing of the substrates. Typically, whitening agentsmay be found in laundry detergents, fabric softeners, or rinse aids andare therefore applied to textile substrates during the launderingprocess. However, it is important that whitening agents function tobrighten treated textile substrates without causing undesirable stainingof the textile substrates.

Cellulosic substrates, in particular, tend to exhibit a yellow hue afterexposure to light, air, and/or soiling. This yellowness is oftendifficult to reverse by normal laundering procedures. As a result, thereexists a need for improved whitening agents which are capable ofeliminating the yellowness exhibited by ageing cellulosic substrates. Byutilizing such improved whitening agents, the life of the textilesubstrates, such as clothing articles, table linens, etc., may beextended.

The present invention offers advantages over U.S. Pat. No. 4,137,243,5,039,782 and US Patent Application Publication No. 2005/0288206 as thisinvention takes advantage of compounds having a Hansen SolubilityParameter of less than or equal to about 17 MPa^(0.5) and which emitlight with wavelengths in the range of blue, red, violet, purple, orcombinations thereof upon exposure to ultraviolet light (or, they absorblight to produce the same shades) in order to neutralize the yellownessof cellulosic substrates. These compounds function ideally as whiteningagents for cellulosic substrates and may be incorporated into laundrydetergent formulations for use by consumers during the launderingprocess.

SUMMARY OF INVENTION

This invention relates to novel whitening agents for cellulosicsubstrates. The whitening agents are comprised of at least twocomponents: at least one chromophore component and at least onepolymeric component. Suitable chromophore components generally fluoresceblue, red, violet, or purple color when exposed to ultraviolet light, orthey may absorb light to reflect these same shades. The whitening agentsare further characterized by having a dispersion component value of theHansen Solubility Parameter of less than or equal to about 17 MPa^(0.5).This invention also relates to laundry care compositions including butnot limited to liquid and/or powder laundry detergent formulations andrinse added fabric softening (RAFS) compositions that comprise suchwhitening agents.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical representation of dispersion component values ofthe Hansen Solubility Parameter versus CIELab b* values for variouswhitening agents after 1 rinse cycle.

DETAILED DESCRIPTION

As used herein, “cellulosic substrates” are intended to include anysubstrate which comprises at least a majority by weight of cellulose.Cellulose may be found in wood, cotton, linen, jute, and hemp.Cellulosic substrates may be in the form of powders, fibers, pulp andarticles formed from powders, fibers and pulp. Cellulosic fibers,include, without limitation, cotton, rayon (regenerated cellulose),acetate (cellulose acetate), triacetate (cellulose triacetate), andmixtures thereof. Articles formed from cellulosic fibers include textilearticles such as fabrics. Articles formed from pulp include paper.

As used herein, the term “laundry care composition” includes, unlessotherwise indicated, granular, powder, liquid, gel, paste, bar formand/or flake type washing agents and/or fabric treatment compositions.

As used herein, the term “fabric treatment composition” includes, unlessotherwise indicated, fabric softening compositions, fabric enhancingcompositions, fabric freshening compositions and combinations there of.Such compositions may be, but need not be rinse added compositions.

As used herein, the articles including “the”, “a” and “an” when used ina claim, are understood to mean one or more of what is claimed ordescribed.

As used herein, the terms “include”, “includes” and “including” aremeant to be non-limiting. The test methods disclosed in the Test MethodsSection of the present application should be used to determine therespective values of the parameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

All documents cited are, in relevant part, incorporated herein byreference; the citation of any document is not to be construed as anadmission that it is prior art with respect to the present invention.

The whitening agents of the present invention may be dyes, pigments, orpolymeric colorants comprising a chromophore constituent and a polymericconstituent. The chromophore constituent is characterized in that itemits or absorbs wavelength in the range of blue, red, violet, purple,or combinations thereof upon exposure to light. Preferably, thechromophore constituent exhibits an absorbance spectrum value from about520 nanometers to about 640 nanometers in water, and more preferablyfrom about 570 nanometers to about 610 nanometers in water. Preferably,the chromophore constituent exhibits an emission spectrum value fromabout 400 nanometers to about 480 nanometers in water.

Examples of suitable polymeric constituents include polyoxyalkylenechains having multiple repeating units. Preferably the polymericconstituents include polyoxyalkylene chains having from 2 to about 20repeating units, and more preferably from 2 to about 10 or even fromabout 4 to about 6 repeating units. Non-limiting examples ofpolyoxyalkylene chains include ethylene oxide, propylene oxide, glycidoloxide, butylene oxide and mixtures thereof.

The whitening agent of the present invention may be characterized by thefollowing structure:

Wherein R₁ and R₂ can independently be selected from:

-   -   a) [CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H]        -   wherein R′ is selected from the group consisting of H, CH₃,            CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is            selected from the group consisting of H, CH₂O(CH₂CH₂O)_(z)H,            and mixtures thereof; wherein x+y≦5; wherein y≧1; and            wherein z=0 to 5;    -   b) R₁=alkyl, aryl or aryl alkyl and        R₂═[(CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H]        -   wherein R′ is selected from the group consisting of H, CH₃,            CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is            selected from the group consisting of H, CH₂O(CH₂CH₂O)_(z)H,            and mixtures thereof; wherein x+y≦10; wherein y≧1; and        -   wherein z=0 to 5;    -   c) R₁═[CH₂CH₂(OR₃)CH₂OR₄] and R₂═[CH₂CH₂(OR₃)CH₂O R₄]        -   wherein R₃ is selected from the group consisting of H,            (CH₂CH₂O)_(z)H, and mixtures thereof; and wherein z=0 to 10;        -   wherein R₄ is selected from the group consisting of            (C₁-C₁₆)alkyl, aryl groups, and mixtures thereof; and

d) wherein R₁ and R₂ can independently be selected from the aminoaddition product of styrene oxide, glycidyl methyl ether, isobutylglycidyl ether, isopropylglycidyl ether, t-butyl glycidyl ether,2-ethylhexylgycidyl ether, and glycidylhexadecyl ether, followed by theaddition of from 1 to 10 alkylene oxide units.

The whitening agent of the present invention may also be characterizedby the following structure:

Wherein R₁ and R₂ are independently selected from:

-   -   a) [CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H]        -   wherein R′ is selected from the group consisting of H, CH₃,            CH₂O(CH₂CH₂O)_(z)H; wherein R″ is selected from the group            consisting of H, CH₂O(CH₂CH₂O)_(z)H; wherein x+y≦5;        -   wherein y≧1; and wherein z=0 to 5;    -   b) R₁=alkyl, aryl or aryl alkyl and        R₂═[CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H]        -   wherein R′ is selected from the group consisting of H, CH₃,            CH₂O(CH₂CH₂O)_(z)H; wherein R″ is selected from the group            consisting of H, CH₂O(CH₂CH₂O)_(z)H; wherein x+y≦10;        -   wherein y≧1; and wherein z=0 to 5;    -   c) R₁═[CH₂CH₂(OR₃)CH₂OR₄] and R₂═[CH₂CH₂(OR₃)CH₂O R₄]        -   wherein R₃ is selected from the group consisting of H,            (CH₂CH₂O)_(z)H; and wherein z=0 to 10;        -   wherein R₄ is selected from the group consisting of            (C₁-C₁₆)alkyl , aryl groups; and    -   d) wherein R₁ and R₂ can independently be selected from the        amino addition product of styrene oxide, glycidyl methyl ether,        isobutyl glycidyl ether, isopropylglycidyl ether, t-butyl        glycidyl ether, 2-ethylhexylgycidyl ether, and glycidylhexadecyl        ether, followed by the addition of from 1 to 10 alkylene oxide        units; and

Wherein R₅, R₆, R₇ and R₈ are independently selected from the groupconsisting of hydrogen, alkyl, oxyalkyl, oxyaryl, sulfonaidoalkyl,sulfonamidoaryl, amidoalkyl, amidodialkyl, amidoaryl, amidodiaryl,halogen, thioalkyl and thioaryl.

A preferred whitening agent of the present invention may becharacterized by the following structure:

wherein R′ is selected from the group consisting of H, CH₃,CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is selected fromthe group consisting of H, CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof;wherein x+y≦5; wherein y≧1; and wherein z=0 to 5.

Another characteristic of the whitening agent of the present inventionis its affinity for cellulosic material. Affinity may be determinedquantitatively from using the dispersion force component of the HansenSolubility Parameter. The Hansen Solubility Parameter is a threecomponent measuring system that includes a dispersion force component(δ_(d)), a hydrogen bonding component (δ_(h)), and a polar component(δ_(p)). The Hansen Solubility Parameter “δ” is derived from the factthat the total cohesive energy, which is the energy required to breakall the cohesive bonds, is the combination of the dispersion forces (d),the molecular dipole forces (p), and the hydrogen bonding forces (h)according to the following equation:

δ²=δ_(d) ²+δ_(p) ²+δ_(h) ².   (1)

Dispersion forces are weak attractive forces between non-polarmolecules. The magnitude of these forces depends on the polarizabilityof the molecule, and the dispersion Hansen Solubility Parameter, δ_(d),typically increases with increasing volume (and size) of the molecule,all other properties being roughly equal. The parameter “δ_(p)”increases with increasing polarity of the molecule.

Hansen Solubility Parameters are calculated at 25° C. with ChemSW'sMolecular Modeling Pro v.6.1.9 software package which uses anunpublished proprietary algorithm that is based on values published inthe Handbook of Solubility Parameters and Other Parameters by Allan F.M. Barton (CRC Press, 1983) for solvents obtained experimentally byHansen. All values of the Hansen Solubility Parameter reported hereinare in units of MPa^(0.5) (square root of megaPascals). Hansenoriginally determined the solubility parameter of solvents for polymersolutions. While Hansen Solubility Parameter calculation has beenapplied successfully to a wide range of applications such as solubilityof biological materials, characterization of pigments, fillers andfibers, etc., it has not heretofore been adapted to polymeric colorants.

Thus, for the effective whitening agents of the present invention, it ispreferable that the dispersion force component of the Hansen SolubilityParameter, 5_(d), is less than or equal to about 17, and more preferablyless than or equal to about 15. It may also be desirable that thedispersion force component of the Hansen Solubility Parameter is fromabout 12 to about 17, and more preferably from about 12 to about 15.

While the affinity of the whitening agent to the cellulosic materialappears to correlate very well with the Hansen Solubility DispersionComponent parameter, the invention is not limited to the use of δ_(d).Other molecular descriptors, which are directly or indirectly related toδ_(d) such as, for example, polarizability, radius of gyration,molecular volume, and Jurs descriptors based on partial atomic chargesmapped on solvent-accessible surface area, were also considered.However, the goodness of fit of the univariate correlations of theaffinity with these descriptors was not as good as with δ_(d).

Without being bound by theory, it is believed that the affinity of thewhitening agents for the cellulose substrates may be ascribed to Van derWaals forces, the attractive forces that exist between electricallyneutral molecules in close proximity to one another. It is alsopostulated that if the cellulose substrate is comprised of porousregions, the whitening agent, or portions thereof, may be physicallytrapped in the pores of the cellulose, depending on the size of themolecule as compared to the diameter of the pores. This physicalentrapment may provide some level of durability to protect the whiteningagent from being easily removed form the cellulose substrate uponexposure to washing or rinsing.

The whitening agent's described in the present specification may beincorporated into a laundry care composition including but not limitedto laundry detergents and fabric care compositions. Such compositionscomprise one or more of said whitening agents and a laundry careingredient. The whitening agent may be added to cellulose substratesusing a variety of application techniques. For application tocellulose-containing textile substrates, the whitening agent ispreferably included as an additive in laundry detergent. Thus,application to the cellulose-containing textile substrate actuallyoccurs when a consumer adds laundry detergent to a washing machine.Similarly, RAFS compositions are typically added in the rinse cycle,which is after the detergent solution has been used and replaced withthe rinsing solution in typical laundering processes. For application tocellulosic paper substrates, the whitening agent may be added to thepaper pulp mixture prior to formation of the final paper product.

The laundry care compositions including laundry detergents may be insolid or liquid form, including a gel form. The laundry detergentcomposition comprises a surfactant in an amount sufficient to providedesired cleaning properties.

The whitening agent may be present in the laundry detergent compositionin an amount from about 0.0001% to about 10% by weight of thecomposition, more preferably from about 0.0001% to about 5% by weight ofthe composition, and even more preferably from about 0.0001% to about 1%by weight of the composition.

The laundry detergent composition comprises a surfactant in an amountsufficient to provide desired cleaning properties. In one embodiment,the laundry detergent composition comprises, by weight, from about 5% toabout 90% of the surfactant, and more specifically from about 5% toabout 70% of the surfactant, and even more specifically from about 5% toabout 40%. The surfactant may comprise anionic, nonionic, cationic,zwitterionic and/or amphoteric surfactants. In a more specificembodiment, the detergent composition comprises anionic surfactant,nonionic surfactant, or mixtures thereof.

Suitable anionic surfactants useful herein can comprise any of theconventional anionic surfactant types typically used in liquid detergentproducts. These include the alkyl benzene sulfonic acids and their saltsas well as alkoxylated or non-alkoxylated alkyl sulfate materials.

Exemplary anionic surfactants are the alkali metal salts of C.sub.10-16alkyl benzene sulfonic acids, preferably C.sub.11-14 alkyl benzenesulfonic acids. Preferably the alkyl group is linear and such linearalkyl benzene sulfonates are known as “LAS”. Alkyl benzene sulfonates,and particularly LAS, are well known in the art. Such surfactants andtheir preparation are described for example in U.S. Pat. Nos. 2,220,099and 2,477,383. Especially preferred are the sodium and potassium linearstraight chain alkylbenzene sulfonates in which the average number ofcarbon atoms in the alkyl group is from about 11 to 14. Sodium C₁₁-C₁₄,e.g., C₁₂, LAS is a specific example of such surfactants.

Another exemplary type of anionic surfactant comprises ethoxylated alkylsulfate surfactants. Such materials, also known as alkyl ether sulfatesor alkyl polyethoxylate sulfates, are those which correspond to theformula: R′—O—(C₂H₄O)_(n)—SO₃M wherein R′ is a C₈-C₂₀ alkyl group, n isfrom about 1 to 20, and M is a salt-forming cation. In a specificembodiment, R′ is C₁₀-C₁₈ alkyl, n is from about 1 to 15, and M issodium, potassium, ammonium, alkylammonium, or alkanolammonium. In morespecific embodiments, R′ is a C₁₂-C₁₆, n is from about 1 to 6 and M issodium.

The alkyl ether sulfates will generally be used in the form of mixturescomprising varying R′ chain lengths and varying degrees of ethoxylation.Frequently such mixtures will inevitably also contain somenon-ethoxylated alkyl sulfate materials, i.e., surfactants of the aboveethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkylsulfates may also be added separately to the compositions of thisinvention and used as or in any anionic surfactant component which maybe present. Specific examples of non-alkoxylated, e.g., non-ethoxylated,alkyl ether sulfate surfactants are those produced by the sulfation ofhigher C₈-C₂₀ fatty alcohols. Conventional primary alkyl sulfatesurfactants have the general formula: ROSO₃-M⁺ wherein R is typically alinear C₈-C₂₀ hydrocarbyl group, which may be straight chain or branchedchain, and M is a water-solubilizing cation. In specific embodiments, Ris a C₁₀-C₁₅ alkyl, and M is alkali metal, more specifically R isC₁₂-C₁₄ and M is sodium.

Specific, non-limiting examples of anionic surfactants useful hereininclude: a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS); b) C₁₀-C₂₀ primary,branched-chain and random alkyl sulfates (AS);

c) C₁₀-C₁₈ secondary (2,3) alkyl sulfates having formulae (I) and (II):wherein M in formulae (I) and (II) is hydrogen or a cation whichprovides charge neutrality, and all M units, whether associated with asurfactant or adjunct ingredient, can either be a hydrogen atom or acation depending upon the form isolated by the artisan or the relativepH of the system wherein the compound is used, with non-limitingexamples of preferred cations including sodium, potassium, ammonium, andmixtures thereof, and x is an integer of at least about 7, preferably atleast about 9, and y is an integer of at least 8, preferably at leastabout 9; d) C₁₀-C₁₈ alkyl alkoxy sulfates (AE.sub.xS) wherein preferablyx is from 1-30; e) C₁₀-C₁₈ alkyl alkoxy carboxylates preferablycomprising 1-5 ethoxy units; f) mid-chain branched alkyl sulfates asdiscussed in U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443; g)mid-chain branched alkyl alkoxy sulfates as discussed in U.S. Pat. No.6,008,181 and U.S. Pat. No. 6,020,303; h) modified alkylbenzenesulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242, WO 99/05244,WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO00/23548; i) methyl ester sulfonate (MES); and j) alpha-olefin sulfonate(AOS).

Suitable nonionic surfactants useful herein can comprise any of theconventional nonionic surfactant types typically used in liquiddetergent products. These include alkoxylated fatty alcohols and amineoxide surfactants. Preferred for use in the liquid detergent productsherein are those nonionic surfactants which are normally liquid.

Suitable nonionic surfactants for use herein include the alcoholalkoxylate nonionic surfactants. Alcohol alkoxylates are materials whichcorrespond to the general formula: R¹(C_(m)H_(2m)O)_(n)OH wherein R¹ isa C₈-C₁₆ alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.Preferably R¹ is an alkyl group, which may be primary or secondary, thatcomprises from about 9 to 15 carbon atoms, more preferably from about 10to 14 carbon atoms. In one embodiment, the alkoxylated fatty alcoholswill also be ethoxylated materials that contain from about 2 to 12ethylene oxide moieties per molecule, more preferably from about 3 to 10ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol materials useful in the liquid detergentcompositions herein will frequently have a hydrophilic-lipophilicbalance (HLB) which ranges from about 3 to 17. More preferably, the HLBof this material will range from about 6 to 15, most preferably fromabout 8 to 15. Alkoxylated fatty alcohol nonionic surfactants have beenmarketed under the tradenames Neodol and Dobanol by the Shell ChemicalCompany.

Another suitable type of nonionic surfactant useful herein comprises theamine oxide surfactants. Amine oxides are materials which are oftenreferred to in the art as “semi-polar” nonionics. Amine oxides have theformula: R(EO)_(x)(PO)_(y)(BO)_(z)N(O)(CH₂R′)₂.qH₂O. In this formula, Ris a relatively long-chain hydrocarbyl moiety which can be saturated orunsaturated, linear or branched, and can contain from 8 to 20,preferably from 10 to 16 carbon atoms, and is more preferably C₁₂-C₁₆primary alkyl. R′ is a short-chain moiety, preferably selected fromhydrogen, methyl and —CH₂OH. When x+y+z is different from 0, EO isethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxidesurfactants are illustrated by C₁₂-C₁₄ alkyldimethyl amine oxide.

Non-limiting examples of nonionic surfactants include: a) C₁₂-C₁₈ alkylethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C₆-C₁₂alkyl phenol alkoxylates wherein the alkoxylate units are a mixture ofethyleneoxy and propyleneoxy units; c) C₁₂-C₁₈ alcohol and C₆-C₁₂ alkylphenol condensates with ethylene oxide/propylene oxide block polymerssuch as Pluronic® from BASF; d) C₁₄-C₂₂ mid-chain branched alcohols, BA,as discussed in U.S. Pat. No. 6,150,322; e) C₁₄-C₂₂ mid-chain branchedalkyl alkoxylates, BAE_(x), wherein x if from 1-30, as discussed in U.S.Pat. No. 6,153,577, U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,093,856;f) Alkylpolysaccharides as discussed in U.S. Pat. No. 4,565,647 toLlenado, issued Jan. 26, 1986; specifically alkylpolyglycosides asdiscussed in U.S. Pat. No. 4,483,780 and U.S. Pat. No. 4,483,779; g)Polyhydroxy fatty acid amides as discussed in U.S. Pat. No. 5,332,528,WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) ethercapped poly(oxyalkylated) alcohol surfactants as discussed in U.S. Pat.No. 6,482,994 and WO 01/42408.

In the laundry detergent compositions herein, the detersive surfactantcomponent may comprise combinations of anionic and nonionic surfactantmaterials. When this is the case, the weight ratio of anionic tononionic will typically range from 10:90 to 90:10, more typically from30:70 to 70:30.

Cationic surfactants are well known in the art and non-limiting examplesof these include quaternary ammonium surfactants, which can have up to26 carbon atoms. Additional examples include a) alkoxylate quaternaryammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; b)dimethyl hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No.6,004,922; c) polyamine cationic surfactants as discussed in WO98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; d)cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042,4,239,660 4,260,529 and U.S. Pat. No. 6,022,844; and e) aminosurfactants as discussed in U.S. Pat. No. 6,221,825 and WO 00/47708,specifically amido propyldimethyl amine (APA).

Non-limiting examples of zwitterionic surfactants include derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary andtertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 throughcolumn 22, line 48, for examples of zwitterionic surfactants; betaine,including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine,C₈ to C₁₈ (preferably C₁₂ to C₁₈) amine oxides and sulfo and hydroxybetaines, such as N-alkyl-N,N-dimethylammino-1-propane sulfonate wherethe alkyl group can be C₈ to C₁₈, preferably C₁₀ to C₁₄.

Non-limiting examples of ampholytic surfactants include aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents comprises at least about 8 carbon atoms, typically fromabout 8 to about 18 carbon atoms, and at least one comprises an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column19, lines 18-35, for examples of ampholytic surfactants.

As noted, the compositions may be in the form of a solid, either intablet or particulate form, including, but not limited to particles,flakes, or the like, or the compositions may be in the form of a liquid.The liquid detergent compositions comprise an aqueous, non-surfaceactive liquid carrier. Generally, the amount of the aqueous, non-surfaceactive liquid carrier employed in the compositions herein will beeffective to solubilize, suspend or disperse the composition components.For example, the compositions may comprise, by weight, from about 5% toabout 90%, more specifically from about 10% to about 70%, and even morespecifically from about 20% to about 70% of the aqueous, non-surfaceactive liquid carrier.

The most cost effective type of aqueous, non-surface active liquidcarrier is, of course, water itself. Accordingly, the aqueous,non-surface active liquid carrier component will generally be mostly, ifnot completely, comprised of water. While other types of water-miscibleliquids, such alkanols, diols, other polyols, ethers, amines, and thelike, have been conventionally been added to liquid detergentcompositions as co-solvents or stabilizers, for purposes of the presentinvention, the utilization of such water-miscible liquids should beminimized to hold down composition cost. Accordingly, the aqueous liquidcarrier component of the liquid detergent products herein will generallycomprise water present in concentrations ranging from about 5% to about90%, more preferably from about 20% to about 70%, by weight of thecomposition.

Detergent compositions may also contain bleaching agents. Suitablebleaching agents include, for example, hydrogen peroxide sources, suchas those described in detail in the herein incorporated Kirk Othmer'sEncyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons),Vol. 4, pp. 271-300 “Bleaching Agents (Survey).” These hydrogen peroxidesources include the various forms of sodium perborate and sodiumpercarbonate, including various coated and modified forms of thesecompounds.

The preferred source of hydrogen peroxide used herein can be anyconvenient source, including hydrogen peroxide itself. For example,perborate, e.g., sodium perborate (any hydrate but preferably the mono-or tetra-hydrate), sodium carbonate peroxyhydrate or equivalentpercarbonate salts, sodium pyrophosphate peroxyhydrate, ureaperoxyhydrate, or sodium peroxide can be used herein. Also useful aresources of available oxygen such as persulfate bleach (e.g., OXONE,manufactured by DuPont). Sodium perborate monohydrate and sodiumpercarbonate are particularly preferred. Mixtures of any convenienthydrogen peroxide sources can also be used.

A suitable percarbonate bleach comprises dry particles having an averageparticle size in the range from about 500 micrometers to about 1,000micrometers, not more than about 10% by weight of said particles beingsmaller than about 200 micrometers and not more than about 10% by weightof said particles being larger than about 1,250 micrometers. Optionally,the percarbonate can be coated with a silicate, borate or water-solublesurfactants. Percarbonate is available from various commercial sourcessuch as FMC, Solvay and Tokai Denka.

Compositions of the present invention may also comprise as the bleachingagent a chlorine-type bleaching material. Such agents are well known inthe art, and include for example sodium dichloroisocyanurate (“NaDCC”).However, chlorine-type bleaches are less preferred for compositionswhich comprise enzymes.

(a) Bleach Activators—Preferably, the peroxygen bleach component in thecomposition is formulated with an activator (peracid precursor). Theactivator is present at levels of from about 0.01%, preferably fromabout 0.5%, more preferably from about 1% to about 15%, preferably toabout 10%, more preferably to about 8%, by weight of the composition. Ableach activator as used herein is any compound which, when used inconjunction with a hydrogen peroxide, source leads to the in situproduction of the peracid corresponding to the bleach activator. Variousnon-limiting examples of activators are disclosed in U.S. Pat. Nos.5,576,282; 4,915,854 and 4,412,934. See also U.S. Pat. No. 4,634,551 forother typical bleaches and activators useful herein.

Preferred activators are selected from the group consisting oftetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL),4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam,benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS),phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C₁₀-OBS),benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (C₈-OBS),perhydrolyzable esters and mixtures thereof, most preferablybenzoylcaprolactam and benzoylvalerolactam. Particularly preferredbleach activators in the pH range from about 8 to about 11 are thoseselected having an OBS or VL leaving group.

Preferred hydrophobic bleach activators include, but are not limited to,nonanoyloxybenzene-sulphonate (NOBS); 4-[N-(nonanoyl) aminohexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS), an example ofwhich is described in U.S. Pat. No. 5,523,434;dodecanoyloxybenzenesulphonate (LOBS or C₁₂-OBS);10-undecenoyloxybenzenesulfonate (UDOBS or C₁₁-OBS with unsaturation inthe 10 position); and decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are those described in U.S. Pat. No.5,998,350 to Burns et al.; U.S. Pat. No. 5,698,504 to Christie et al.;U.S. Pat. No. 5,695,679 to Christie et al.; U.S. Pat. No. 5,686,401 toWilley et al.; U.S. Pat. No. 5,686,014 to Hartshorn et al.; U.S. Pat.No. 5,405,412 to Willey et al.; U.S. Pat. No. 5,405,413 to Willey etal.; U.S. Pat. No. 5,130,045 to Mitchel et al.; and U.S. Pat. No.4,412,934 to Chung et al., and copending patent application Ser. No.08/064,564, all of which are incorporated herein by reference.

The mole ratio of peroxygen source (as AvO) to bleach activator in thepresent invention generally ranges from at least 1:1, preferably fromabout 20:1, more preferably from about 10:1 to about 1:1, preferably toabout 3:1.

Quaternary substituted bleach activators may also be included. Thepresent laundry compositions preferably comprise a quaternarysubstituted bleach activator (QSBA) or a quaternary substituted peracid(QSP, preferably a quaternary substituted percarboxylic acid or aquaternary substituted peroxyimidic acid); more preferably, the former.Preferred QSBA structures are further described in U.S. Pat. No.5,686,015 to Willey et al.; U.S. Pat. No. 5,654,421 to Taylor et al.;U.S. Pat. No. 5,460,747 to Gosselink et al.; U.S. Pat. No. 5,584,888 toMiracle et al.; U.S. Pat. No. 5,578,136 to Taylor et al.; all of whichare incorporated herein by reference.

Highly preferred bleach activators useful herein are amide-substitutedas described in U.S. Pat. Nos. 5,698,504; 5,695,679; and 5,686,014, eachof which are cited herein above. Preferred examples of such bleachactivators include: (6-octanamidocaproyl) oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate and mixtures thereof.

Other useful activators are disclosed in U.S. Pat. Nos. 5,698,504;5,695,679; and 5,686,014, each of which is cited herein above, and inU.S. Pat. No. 4,966,723 to Hodge et al. These activators includebenzoxazin-type activators, such as a C₆H₄ ring to which is fused in the1,2-positions a moiety —C(O)OC(R¹)═N—.

Nitriles, such as acetonitriles and/or ammonium nitriles and otherquaternary nitrogen containing nitriles, are another class of activatorsthat are useful herein. Non-limiting examples of such nitrile bleachactivators are described in U.S. Pat. Nos. 6,133,216; 3,986,972;6,063,750; 6,017,464; 5,958,289; 5,877,315; 5,741,437; 5,739,327;5,004,558; and in EP Nos. 790 244, 775 127, 1 017 773, 1 017 776; and inWO 99/14302, WO 99/14296, WO96/40661, all of which are incorporatedherein by reference.

Depending on the activator and precise application, good bleachingresults can be obtained from bleaching systems having an in-use pH offrom about 6 to about 13, and preferably from about 9.0 to about 10.5.Typically, for example, activators with electron-withdrawing moietiesare used for near-neutral or sub-neutral pH ranges. Alkalis andbuffering agents can be used to secure such pH.

Acyl lactam activators, as described in U.S. Pat. Nos. 5,698,504;5,695,679 and 5,686,014, each of which is cited herein above, are veryuseful herein, especially the acyl caprolactams (see for example WO94-28102 A) and acyl valerolactams (see U.S. Pat. No. 5,503,639 toWilley et al. incorporated herein by reference).

(b) Organic Peroxides, especially Diacyl Peroxides—These are extensivelyillustrated in Kirk Othmer, Encyclopedia of Chemical Technology, Vol.17, John Wiley and Sons, 1982 at pages 27-90 and especially at pages63-72, all incorporated herein by reference. If a diacyl peroxide isused, it will preferably be one which exerts minimal adverse impact onfabric care, including color care.

(c) Metal-Containing Bleach Catalysts—The compositions and methods ofthe present invention can also optionally include metal-containingbleach catalysts, preferably manganese and cobalt-containing bleachcatalysts.

One type of metal-containing bleach catalyst is a catalyst systemcomprising a transition metal cation of defined bleach catalyticactivity (such as copper, iron, titanium, ruthenium tungsten,molybdenum, or manganese cations), an auxiliary metal cation havinglittle or no bleach catalytic activity (such as zinc or aluminumcations), and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243 to Bragg.

Manganese Metal Complexes—If desired, the compositions herein can becatalyzed by means of a manganese compound. Such compounds and levels ofuse are well known in the art and include, for example, themanganese-based catalysts disclosed in U.S. Pat. Nos. 5,576,282;5,246,621; 5,244,594; 5,194,416; and 5,114,606; and European Pat. App.Pub. Nos. 549,271 A1; 549,272 A1; 544,440 A2; and 544,490 A1. Preferredexamples of these catalysts include Mn^(IV)₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂, Mn^(III)₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂,Mn^(IV) ₄(u-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn^(III)Mn^(IV)₄(u-O)₁(u-OAc)₂-(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃,Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃(PF₆), andmixtures thereof. Other metal-based bleach catalysts include thosedisclosed in U.S. Pat. Nos. 4,430,243 and 5,114,611. The use ofmanganese with various complex ligands to enhance bleaching is alsoreported in the following: U.S. Pat. Nos. 4,728,455; 5,284,944;5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

Cobalt Metal Complexes—Cobalt bleach catalysts useful herein are known,and are described, for example, in U.S. Pat. Nos. 5,597,936; 5,595,967;and 5,703,030; and M. L. Tobe, “Base Hydrolysis of Transition-MetalComplexes”, Adv. lnorg. Bioinorg. Mech., (1983), 2, pages 1-94. The mostpreferred cobalt catalyst useful herein are cobalt pentaamine acetatesalts having the formula [Co(NH₃)₅OAc] T_(y), wherein “OAc” representsan acetate moiety and “T_(y)” is an anion, and especially cobaltpentaamine acetate chloride, [Co(NH₃)₆OAc]Cl₂; as well as[Co(NH₃)₅OAc](OAc)₂; [Co(NH₃)₅OAc](PF₆)₂; [Co(NH₃)₅OAc]SO₄);[Co(NH₃)₅OAc](BF₄)₂; and [Co(NH₃)₅OAc](NO₃)₂ (herein “PAC”).

These cobalt catalysts are readily prepared by known procedures, such astaught for example in U.S. Pat. Nos. 6,302,921; 6,287,580; 6,140,294;5,597,936; 5,595,967; and 5,703,030; in the Tobe article and thereferences cited therein; and in U.S. Pat. No. 4,810,410; J. Chem. Ed.(1989), 66 (12), 1043-45; The Synthesis and Characterization ofInorganic Compounds, W. L. Jolly (Prentice-Hall; 1970), pp. 461-3;Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982);Inorg. Chem., 18, 2023-2025 (1979); lnorg. Synthesis, 173-176 (1960);and Journal of Physical Chemistry, 56, 22-25 (1952).

Transition Metal Complexes of Macropolycyclic Rigid Ligands—Compositionsherein may also suitably include as bleach catalyst a transition metalcomplex of a macropolycyclic rigid ligand. The amount used is acatalytically effective amount, suitably about 1 ppb or more, forexample up to about 99.9%, more typically about 0.001 ppm or more,preferably from about 0.05 ppm to about 500 ppm (wherein “ppb” denotesparts per billion by weight and “ppm” denotes parts per million byweight).

Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which aresuitable for use in the invention compositions can in general includeknown compounds where they conform with the definition herein, as wellas, more preferably, any of a large number of novel compounds expresslydesigned for the present laundry or laundry uses, and are non-limitinglyillustrated by any of the following:

-   -   Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane        Manganese(II)    -   Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane        Manganese(II)    -   Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)        Hexafluorophosphate    -   Diaquo-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)        Hexafluorophosphate    -   Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane        Manganese(III) Hexafluorophosphate    -   Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)        Tetrafluoroborate    -   Dichloro-5,12-dimethyl-1,5,8,12 tetraazabicyclo[6.6.2]hexadecane        Manganese(III) Hexafluorophosphate    -   Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III)        Hexafluorophosphate    -   Dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza        bicyclo[6.6.2]hexadecane Manganese(II)    -   Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)    -   Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane        Manganese(II)    -   Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane        Manganese(II)    -   Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane        Manganese(II).

As a practical matter, and not by way of limitation, the compositionsand methods herein can be adjusted to provide on the order of at leastone part per hundred million of the active bleach catalyst species inthe composition comprising a lipophilic fluid and a bleach system, andwill preferably provide from about 0.01 ppm to about 25 ppm, morepreferably from about 0.05 ppm to about 10 ppm, and most preferably fromabout 0.1 ppm to about 5 ppm, of the bleach catalyst species in thecomposition comprising a lipophilic fluid and a bleach system.

(d) Bleach Boosting Compounds—The compositions herein may comprise oneor more bleach boosting compounds. Bleach boosting compounds provideincreased bleaching effectiveness in lower temperature applications. Thebleach boosters act in conjunction with conventional peroxygen bleachingsources to provide increased bleaching effectiveness. This is normallyaccomplished through in situ formation of an active oxygen transferagent such as a dioxirane, an oxaziridine, or an oxaziridinium.Alternatively, preformed dioxiranes, oxaziridines and oxaziridiniums maybe used.

Among suitable bleach boosting compounds for use in accordance with thepresent invention are cationic imines, zwitterionic imines, anionicimines and/or polyionic imines having a net charge of from about +3 toabout −3, and mixtures thereof. These imine bleach boosting compounds ofthe present invention include those of the general structure:

where R¹-R⁴ may be a hydrogen or an unsubstituted or substituted radicalselected from the group consisting of phenyl, aryl, heterocyclic ring,alkyl and cycloalkyl radicals.

Among preferred bleach boosting compounds are zwitterionic bleachboosters, which are described in U.S. Pat. Nos. 5,576,282 and 5,718,614.Other bleach boosting compounds include cationic bleach boostersdescribed in U.S. Pat. Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826;5,482,515; 5,550,256; and WO 95/13351, WO 95/13352, and WO 95/13353.

Peroxygen sources are well-known in the art and the peroxygen sourceemployed in the present invention may comprise any of these well knownsources, including peroxygen compounds as well as compounds, which underconsumer use conditions, provide an effective amount of peroxygen insitu. The peroxygen source may include a hydrogen peroxide source, thein situ formation of a peracid anion through the reaction of a hydrogenperoxide source and a bleach activator, preformed peracid compounds ormixtures of suitable peroxygen sources. Of course, one of ordinary skillin the art will recognize that other sources of peroxygen may beemployed without departing from the scope of the invention. The bleachboosting compounds, when present, are preferably employed in conjunctionwith a peroxygen source in the bleaching systems of the presentinvention.

(e) Preformed Peracids—Also suitable as bleaching agents are preformedperacids. The preformed peracid compound as used herein is anyconvenient compound which is stable and which under consumer useconditions provides an effective amount of peracid or peracid anion. Thepreformed peracid compound may be selected from the group consisting ofpercarboxylic acids and salts, percarbonic acids and salts, perimidicacids and salts, peroxymonosulfuric acids and salts, and mixturesthereof. Examples of these compounds are described in U.S. Pat. No.5,576,282 to Miracle et al.

One class of suitable organic peroxycarboxylic acids have the generalformula:

-   -   wherein R is an alkylene or substituted alkylene group        containing from 1 to about 22 carbon atoms or a phenylene or        substituted phenylene group, and Y is hydrogen, halogen, alkyl,        aryl, —C(O)OH or —C(O)OOH.

Organic peroxyacids suitable for use in the present invention cancontain either one or two peroxy groups and can be either aliphatic oraromatic. When the organic peroxycarboxylic acid is aliphatic, theunsubstituted peracid has the general formula:

-   -   wherein Y can be, for example, H, CH₃, CH₂Cl, C(O)OH, or        C(O)OOH; and n is an integer from 0 to 20. When the organic        peroxycarboxylic acid is aromatic, the unsubstituted peracid has        the general formula:

-   -   wherein Y can be, for example, hydrogen, alkyl, alkylhalogen,        halogen, C(O)OH or C(O)OOH.

Typical monoperoxy acids useful herein include alkyl and arylperoxyacids such as:

-   -   (i) peroxybenzoic acid and ring-substituted peroxybenzoic acid,        e.g. peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium        salt hexahydrate), and o-carboxybenzamidoperoxyhexanoic acid        (sodium salt);    -   (ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy        acids, e.g. peroxylauric acid, peroxystearic acid,        N-nonanoylaminoperoxycaproic acid (NAPCA),        N,N-(3-octylsuccinoyl)aminoperoxycaproic acid (SAPA) and        N,N-phthaloylaminoperoxycaproic acid (PAP);    -   (iii) amidoperoxyacids, e.g. monononylamide of either        peroxysuccinic acid (NAPSA) or of peroxyadipic acid (NAPAA).

Typical diperoxyacids useful herein include alkyl diperoxyacids andaryldiperoxyacids, such as:

-   -   (i) 1,12-diperoxydodecanedioic acid;    -   (ii) 1,9-diperoxyazelaic acid;    -   (iii) diperoxybrassylic acid; diperoxysebacic acid and        diperoxyisophthalic acid;    -   (iv) 2-decyldiperoxybutane-1,4-dioic acid;    -   (v) 4,4′-sulfonylbisperoxybenzoic acid.

Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781 toHartman and U.S. Pat. No. 4,634,551 to Burns et al.; European PatentApplication 0,133,354 to Banks et al.; and U.S. Pat. No. 4,412,934 toChung et al. Sources also include 6-nonylamino-6-oxoperoxycaproic acidas described in U.S. Pat. No. 4,634,551 to Burns et al. Persulfatecompounds such as for example OXONE, manufactured commercially by E.I.DuPont de Nemours of Wilmington, Del. can also be employed as a suitablesource of peroxymonosulf uric acid. PAP is disclosed in, for example,U.S. Pat. Nos. 5,487,818; 5,310,934; 5,246,620; 5,279,757 and 5,132,431.

(f) Photobleaches—Suitable photobleaches for use in the treatingcompositions of the present invention include, but are not limited to,the photobleaches described in U.S. Pat. Nos. 4,217,105 and 5,916,481.

(g) Enzyme Bleaching—Enzymatic systems may be used as bleaching agents.The hydrogen peroxide may also be present by adding an enzymatic system(i.e. an enzyme and a substrate therefore) which is capable ofgenerating hydrogen peroxide at the beginning or during the washingand/or rinsing process. Such enzymatic systems are disclosed in EPPatent Application 91202655.6 filed Oct. 9, 1991.

The present invention compositions and methods may utilize alternativebleach systems such as ozone, chlorine dioxide and the like. Bleachingwith ozone may be accomplished by introducing ozone-containing gashaving ozone content from about 20 to about 300 g/m³ into the solutionthat is to contact the fabrics. The gas:liquid ratio in the solutionshould be maintained from about 1:2.5 to about 1:6. U.S. Pat. No. 5,346,588 describes a process for the utilization of ozone as an alternativeto conventional bleach systems and is herein incorporated by reference.

The detergent compositions of the present invention may also include anynumber of additional optional ingredients. These include conventionallaundry detergent composition components such as non-tinting dyes,detersive builders, enzymes, enzyme stabilizers (such as propyleneglycol, boric acid and/or borax), suds suppressors, soil suspendingagents, soil release agents, other fabric care benefit agents, pHadjusting agents, chelating agents, smectite clays, solvents,hydrotropes and phase stabilizers, structuring agents, dye transferinhibiting agents, opacifying agents, optical brighteners, perfumes andcoloring agents. The various optional detergent composition ingredients,if present in the compositions herein, should be utilized atconcentrations conventionally employed to bring about their desiredcontribution to the composition or the laundering operation. Frequently,the total amount of such optional detergent composition ingredients canrange from about 0.01% to about 50%, more preferably from about 0.1% toabout 30%, by weight of the composition.

The liquid detergent compositions are in the form of an aqueous solutionor uniform dispersion or suspension of surfactant, whitening agent, andcertain optional other ingredients, some of which may normally be insolid form, that have been combined with the normally liquid componentsof the composition, such as the liquid alcohol ethoxylate nonionic, theaqueous liquid carrier, and any other normally liquid optionalingredients. Such a solution, dispersion or suspension will beacceptably phase stable and will typically have a viscosity which rangesfrom about 100 to 600 cps, more preferably from about 150 to 400 cps.For purposes of this invention, viscosity is measured with a BrookfieldLVDV-II+viscometer apparatus using a #21 spindle.

The liquid detergent compositions herein can be prepared by combiningthe components thereof in any convenient order and by mixing, e.g.,agitating, the resulting component combination to form a phase stableliquid detergent composition. In a preferred process for preparing suchcompositions, a liquid matrix is formed containing at least a majorproportion, and preferably substantially all, of the liquid components,e.g., nonionic surfactant, the non-surface active liquid carriers andother optional liquid components, with the liquid components beingthoroughly admixed by imparting shear agitation to this liquidcombination. For example, rapid stirring with a mechanical stirrer mayusefully be employed. While shear agitation is maintained, substantiallyall of any anionic surfactants and the solid form ingredients can beadded. Agitation of the mixture is continued, and if necessary, can beincreased at this point to form a solution or a uniform dispersion ofinsoluble solid phase particulates within the liquid phase. After someor all of the solid-form materials have been added to this agitatedmixture, particles of any enzyme material to be included, e.g., enzymeprills, are incorporated. As a variation of the composition preparationprocedure hereinbefore described, one or more of the solid componentsmay be added to the agitated mixture as a solution or slurry ofparticles premixed with a minor portion of one or more of the liquidcomponents. After addition of all of the composition components,agitation of the mixture is continued for a period of time sufficient toform compositions having the requisite viscosity and phase stabilitycharacteristics. Frequently this will involve agitation for a period offrom about 30 to 60 minutes.

In an alternate embodiment for forming the liquid detergentcompositions, the whitening agent is first combined with one or moreliquid components to form a whitening agent premix, and this whiteningagent premix is added to a composition formulation containing asubstantial portion, for example more than 50% by weight, morespecifically, more than 70% by weight, and yet more specifically, morethan 90% by weight, of the balance of components of the laundrydetergent composition. For example, in the methodology described above,both the whitening agent premix and the enzyme component are added at afinal stage of component additions. In a further embodiment, thewhitening agent is encapsulated prior to addition to the detergentcomposition, the encapsulated whitening agent is suspended in astructured liquid, and the suspension is added to a compositionformulation containing a substantial portion of the balance ofcomponents of the laundry detergent composition.

As noted previously, the detergent compositions may be in a solid form.Suitable solid forms include tablets and particulate forms, for example,granular particles or flakes. Various techniques for forming detergentcompositions in such solid forms are well known in the art and may beused herein. In one embodiment, for example when the composition is inthe form of a granular particle, the whitening agent is provided inparticulate form, optionally including additional but not all componentsof the laundry detergent composition. The whitening agent particulate iscombined with one or more additional particulates containing a balanceof components of the laundry detergent composition. Further, thewhitening agent, optionally including additional but not all componentsof the laundry detergent composition, may be provided in an encapsulatedform, and the whitening agent encapsulate is combined with particulatescontaining a substantial balance of components of the laundry detergentcomposition.

The compositions of this invention, prepared as hereinbefore described,can be used to form aqueous washing solutions for use in the launderingof fabrics. Generally, an effective amount of such compositions is addedto water, preferably in a conventional fabric laundering automaticwashing machine, to form such aqueous laundering solutions. The aqueouswashing solution so formed is then contacted, preferably underagitation, with the fabrics to be laundered therewith. An effectiveamount of the liquid detergent compositions herein added to water toform aqueous laundering solutions can comprise amounts sufficient toform from about 500 to 7,000 ppm of composition in aqueous washingsolution. More preferably, from about 1,000 to 3,000 ppm of thedetergent compositions herein will be provided in aqueous washingsolution.

Fabric Care Compositions/Rinse Added Fabric Softening Compositions

In another specific embodiment, the whitening agents of the presentinvention may be included in a fabric care composition. The fabric carecomposition may be comprised of at least one whitening agent and a rinseadded fabric softening composition (“RAFS;” also known as rinse addedfabric conditioning compositions). Examples of typical rinse addedsoftening compositions can be found in U.S. Provisional PatentApplication Ser. No. 60/687582 filed on Oct. 8, 2004. The rinse addedfabric softening compositions of the present invention may comprise (a)fabric softening active and (b) a thiazolium dye. The rinse added fabricsoftening composition may comprise from about 1% to about 90% by weightof the FSA, more preferably from about 5% to about 50% by weight of theFSA. The whitening agent may be present in the rinse added fabricsoftening composition in an amount from about 0.5 ppb to about 50 ppm,more preferably from about 0.5 ppm to about 30 ppm.

In one embodiment of the invention, the fabric softening active(hereinafter “FSA”) is a quaternary ammonium compound suitable forsoftening fabric in a rinse step. In one embodiment, the FSA is formedfrom a reaction product of a fatty acid and an aminoalcohol obtainingmixtures of mono-, di-, and, in one embodiment, triester compounds. Inanother embodiment, the FSA comprises one or more softener quaternaryammonium compounds such, but not limited to, as a monoalkyquaternaryammonium compound, a diamido quaternary compound and a diesterquaternary ammonium compound, or a combination thereof.

In one aspect of the invention, the FSA comprises a diester quaternaryammonium (hereinafter “DQA”) compound composition. In certainembodiments of the present invention, the DQA compounds compositionsalso encompasses a description of diamido FSAs and FSAs with mixed amidoand ester linkages as well as the aforementioned diester linkages, allherein referred to as DQA.

A first type of DQA (“DQA (1)”) suitable as a FSA in the present CFSCincludes a compound comprising the formula:

{R_(4-m)—N⁺—[(CH₂)_(n)—Y—R¹]_(m)}X⁻

-   -   wherein each R substituent is either hydrogen, a short chain        C₁-C₆, preferably C₁-C₃ alkyl or hydroxyalkyl group, e.g.,        methyl (most preferred), ethyl, propyl, hydroxyethyl, and the        like, poly (C₂₋₃ alkoxy), preferably polyethoxy, group, benzyl,        or mixtures thereof; each m is 2 or 3; each n is from 1 to about        4, preferably 2; each Y is —O—(O)O—, —C(O)—O—, —NR—C(O)—, or        —C(O)—NR— and it is acceptable for each Y to be the same or        different; the sum of carbons in each R¹, plus one when Y is        —O—(O)O— or —NR—C(O)—, is C₁₂-C₂₂, preferably C₁₄-C₂₀, with each        R¹ being a hydrocarbyl, or substituted hydrocarbyl group; it is        acceptable for R¹ to be unsaturated or saturated and branched or        linear and preferably it is linear; it is acceptable for each R¹        to be the same or different and preferably these are the same;        and X⁻ can be any softener-compatible anion, preferably,        chloride, bromide, methylsulfate, ethylsulfate, sulfate,        phosphate, and nitrate, more preferably chloride or methyl        sulfate. Preferred DQA compounds are typically made by reacting        alkanolamines such as MDEA (methyldiethanolamine) and TEA        (triethanolamine) with fatty acids. Some materials that        typically result from such reactions include        N,N-di(acyl-oxyethyl)-N,N-dimethylammonium chloride or        N,N-di(acyl-oxyethyl)-N,N-methylhydroxyethylammonium        methylsulfate wherein the acyl group is derived from animal        fats, unsaturated, and polyunsaturated, fatty acids, e.g.,        tallow, hardended tallow, oleic acid, and/or partially        hydrogenated fatty acids, derived from vegetable oils and/or        partially hydrogenated vegetable oils, such as, canola oil,        safflower oil, peanut oil, sunflower oil, corn oil, soybean oil,        tall oil, rice bran oil, palm oil, etc.

Non-limiting examples of suitable fatty acids are listed in U.S. Pat.No. 5,759,990 at column 4, lines 45-66. In one embodiment, the FSAcomprises other actives in addition to DQA (1) or DQA. In yet anotherembodiment, the FSA comprises only DQA (1) or DQA and is free oressentially free of any other quaternary ammonium compounds or otheractives. In yet another embodiment, the FSA comprises the precursoramine that is used to produce the DQA.

In another aspect of the invention, the FSA comprises a compound,identified as DTTMAC comprising the formula:

[R_(4-m)—N(+)—R₁ _(m)]A⁻

-   -   wherein each m is 2 or 3, each R¹ is a C₆-C₂₂, preferably        C₁₄-C₂₀, but no more than one being less than about C₁₂ and then        the other is at least about 16, hydrocarbyl, or substituted        hydrocarbyl substituent, preferably C₁₀-C₂₀ alkyl or alkenyl        (unsaturated alkyl, including polyunsaturated alkyl, also        referred to sometimes as “alkylene”), most preferably C₁₂-C₁₈        alkyl or alkenyl, and branch or unbranched. In one embodiment,        the Iodine Value (IV) of the FSA is from about 1 to 70; each R        is H or a short chain C₁-C₆, preferably C₁-C₃ alkyl or        hydroxyalkyl group, e.g., methyl (most preferred), ethyl,        propyl, hydroxyethyl, and the like, benzyl, or (R²O)₂₋₄H where        each R² is a C₁₋₆ alkylene group; and A⁻ is a softener        compatible anion, preferably, chloride, bromide, methylsulfate,        ethylsulfate, sulfate, phosphate, or nitrate; more preferably        chloride or methyl sulfate.

Examples of these FSAs include dialkydimethylammonium salts anddialkylenedimethylammonium salts such as ditallowdimethylammonium andditallowdimethylammonium methylsulfate. Examples of commerciallyavailable dialkylenedimethylammonium salts usable in the presentinvention are di-hydrogenated tallow dimethyl ammonium chloride andditallowdimethyl ammonium chloride available from Degussa under thetrade names Adogen® 442 and Adogen® 470 respectively. In one embodiment,the FSA comprises other actives in addition to DTTMAC. In yet anotherembodiment, the FSA comprises only compounds of the DTTMAC and is freeor essentially free of any other quaternary ammonium compounds or otheractives.

In one embodiment, the FSA comprises an FSA described in U.S. Pat. Pub.No. 2004/0204337 A1, published Oct. 14, 2004 to Corona et al., fromparagraphs 30-79. In another embodiment, the FSA is one described inU.S. Pat. Pub. No. 2004/0229769 A1, published Nov. 18, 2005, to Smith etal., on paragraphs 26-31; or U.S. Pat. No. 6,494,920, at column 1, line51 et seq. detailing an “esterquat” or a quaternized fatty acidtriethanolamine ester salt.

In one embodiment, the FSA is chosen from at least one of the following:ditallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallowdimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methylsulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, orcombinations thereof.

In one embodiment, the FSA may also include amide containing compoundcompositions. Examples of diamide comprising compounds may include butnot limited to methyl-bis(tallowamidoethyl)-2-hydroxyethylammoniummethyl sulfate (available from Degussa under the trade names Varisoft110 and Varisoft 222). An example of an amide-ester containing compoundisN-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl)]-N-methylamine.

Another specific embodiment of the invention provides for a rinse addedfabric softening composition further comprising a cationic starch.Cationic starches are disclosed in US 2004/0204337 A1. In oneembodiment, the rinse added fabric softening composition comprises fromabout 0.1% to about 7% of cationic starch by weight of the fabricsoftening composition. In one embodiment, the cationic starch is HCP401from National Starch.

Suitable Laundry Care Ingredients

While not essential for the purposes of the present invention, thenon-limiting list of laundry care ingredients illustrated hereinafterare suitable for use in the laundry care compositions and may bedesirably incorporated in certain embodiments of the invention, forexample to assist or enhance performance, for treatment of the substrateto be cleaned, or to modify the aesthetics of the composition as is thecase with perfumes, colorants, dyes or the like. It is understood thatsuch ingredients are in addition to the components that were previouslylisted for any particular embodiment. The total amount of such adjunctsmay range from about 0.1% to about 50%, or even from about 1% to about30%, by weight of the laundry care composition.

The precise nature of these additional components, and levels ofincorporation thereof, will depend on the physical form of thecomposition and the nature of the operation for which it is to be used.Suitable laundry care ingredients include, but are not limited to,polymers, for example cationic polymers, surfactants, builders,chelating agents, dye transfer inhibiting agents, dispersants, enzymes,and enzyme stabilizers, catalytic materials, bleach activators,polymeric dispersing agents, clay soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, additional perfume and perfumedelivery systems, structure elasticizing agents, fabric softeners,carriers, hydrotropes, processing aids and/or pigments. In addition tothe disclosure below, suitable examples of such other adjuncts andlevels of use are found in U.S. Pat. Nos. 5,576,282, 6,306,812 B1 and6,326,348 B1 that are incorporated by reference.

As stated, the laundry care ingredients are not essential to Applicants'laundry care compositions. Thus, certain embodiments of Applicants'compositions do not contain one or more of the following adjunctsmaterials: bleach activators, surfactants, builders, chelating agents,dye transfer inhibiting agents, dispersants, enzymes, and enzymestabilizers, catalytic metal complexes, polymeric dispersing agents,clay and soil removal/anti-redeposition agents, brighteners, sudssuppressors, dyes, additional perfumes and perfume delivery systems,structure elasticizing agents, fabric softeners, carriers, hydrotropes,processing aids and/or pigments. However, when one or more adjuncts arepresent, such one or more adjuncts may be present as detailed below:

Surfactants—The compositions according to the present invention cancomprise a surfactant or surfactant system wherein the surfactant can beselected from nonionic and/or anionic and/or cationic surfactants and/orampholytic and/or zwitterionic and/or semi-polar nonionic surfactants.The surfactant is typically present at a level of from about 0.1%, fromabout 1%, or even from about 5% by weight of the cleaning compositionsto about 99.9%, to about 80%, to about 35%, or even to about 30% byweight of the cleaning compositions.

Builders—The compositions of the present invention can comprise one ormore detergent builders or builder systems. When present, thecompositions will typically comprise at least about 1% builder, or fromabout 5% or 10% to about 80%, 50%, or even 30% by weight, of saidbuilder. Builders include, but are not limited to, the alkali metal,ammonium and alkanolammonium salts of polyphosphates, alkali metalsilicates, alkaline earth and alkali metal carbonates, aluminosilicatebuilders polycarboxylate compounds. ether hydroxypolycarboxylates,copolymers of maleic anhydride with ethylene or vinyl methyl ether,1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, andcarboxymethyl-oxysuccinic acid, the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylatessuch as mellitic acid, succinic acid, oxydisuccinic acid, polymaleicacid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid,and soluble salts thereof.

Chelating Agents—The compositions herein may also optionally contain oneor more copper, iron and/or manganese chelating agents. If utilized,chelating agents will generally comprise from about 0.1% by weight ofthe compositions herein to about 15%, or even from about 3.0% to about15% by weight of the compositions herein.

Dye Transfer Inhibiting Agents—The compositions of the present inventionmay also include one or more dye transfer inhibiting agents. Suitablepolymeric dye transfer inhibiting agents include, but are not limitedto, polyvinylpyrrolidone polymers, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Whenpresent in the compositions herein, the dye transfer inhibiting agentsare present at levels from about 0.0001%, from about 0.01%, from about0.05% by weight of the cleaning compositions to about 10%, about 2%, oreven about 1% by weight of the cleaning compositions.

Dispersants—The compositions of the present invention can also containdispersants. Suitable water-soluble organic materials are the homo- orco-polymeric acids or their salts, in which the polycarboxylic acid maycomprise at least two carboxyl radicals separated from each other by notmore than two carbon atoms.

Enzymes—The compositions can comprise one or more detergent enzymeswhich provide cleaning performance and/or fabric care benefits. Examplesof suitable enzymes include, but are not limited to, hemicellulases,peroxidases, proteases, cellulases, xylanases, lipases, phospholipases,esterases, cutinases, pectinases, keratanases, reductases, oxidases,phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,pentosanases, malanases, B-glucanases, arabinosidases, hyaluronidase,chondroitinase, laccase, and amylases, or mixtures thereof. A typicalcombination is a cocktail of conventional applicable enzymes likeprotease, lipase, cutinase and/or cellulase in conjunction with amylase.

Enzyme Stabilizers—Enzymes for use in compositions, for example,detergents can be stabilized by various techniques. The enzymes employedherein can be stabilized by the presence of water-soluble sources ofcalcium and/or magnesium ions in the finished compositions that providesuch ions to the enzymes.

Catalytic Metal Complexes—Applicants' compositions may include catalyticmetal complexes. One type of metal-containing bleach catalyst is acatalyst system comprising a transition metal cation of defined bleachcatalytic activity, such as copper, iron, titanium, ruthenium, tungsten,molybdenum, or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methyl-enephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243.

If desired, the compositions herein can be catalyzed by means of amanganese compound. Such compounds and levels of use are well known inthe art and include, for example, the manganese-based catalystsdisclosed in U.S. Pat. No. 5,576,282.

Cobalt bleach catalysts useful herein are known, and are described, forexample, in U.S. Pat. Nos. 5,597,936 and 5,595,967. Such cobaltcatalysts are readily prepared by known procedures, such as taught forexample in U.S. Pat. Nos. 5,597,936, and 5,595,967.

Compositions herein may also suitably include a transition metal complexof a macropolycyclic rigid ligand—abbreviated as “MRL”. As a practicalmatter, and not by way of limitation, the compositions and cleaningprocesses herein can be adjusted to provide on the order of at least onepart per hundred million of the benefit agent MRL species in the aqueouswashing medium, and may provide from about 0.005 ppm to about 25 ppm,from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about5 ppm, of the MRL in the wash liquor.

Preferred transition-metals in the instant transition-metal bleachcatalyst include manganese, iron and chromium. Preferred MRL's hereinare a special type of ultra-rigid ligand that is cross-bridged such as5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexa-decane.

Suitable transition metal MRLs are readily prepared by known procedures,such as taught for example in WO 00/32601, and U.S. Pat. No. 6,225,464.

EXAMPLES

The following examples are provided to further illustrate the novelwhitening agents of the present invention; however, they are not to beconstrued as limiting the invention as defined in the claims appendedhereto. In fact, it will be apparent to those skilled in the art thatvarious modifications and variations can be made in this inventionwithout departing from the scope or spirit of the invention. All partsand percents given in these examples are by weight unless otherwiseindicated. All values of the Hansen Solubility Parameter reported hereinare in units of MPa^(0.5).

Sample Preparation and Test Methods

A. Sample Preparation

Each sample is prepared by adding 0.5 grams of whitening agent (0.1%based on weight of the cellulosic substrate) to a solution containing 3grams of powdered laundry detergent (AATCC powder laundry detergent) and500 mL of room temperature water. Each colorant loading is corrected forabsorbance to assure equal amount of color units. The formulation isthen combined with 50 grams of cellulose powder (available from Aldrich)and the mixture is agitated for 10 minutes. The mixture is then filteredto separate the cellulose particles from the liquid, and the celluloseparticles are allowed to air dry. Both the cellulose particles and theliquid are measured for color using a Gretag Macbeth Color Eye 7000Aspectrophotometer, as described previously.

The cellulose particles are then placed in a container containing 500 mLof tap water and agitated for 10 minutes. The mixture is filtered toseparate the cellulose particles from the liquid, and the celluloseparticles are again allowed to air dry. Both the cellulose particles andthe liquid are again measured for color using the Gretag Macbeth ColorEye 7000A spectrophotometer. A Control Sample is also prepared thatcontained untreated cellulose particles (no whitening agent added).

The whitening agents shown in Tables 1A and 1B are prepared as describedherein and tested for various parameters. All violet colorants aresynthesized according to the procedure disclosed in U.S. Pat. No.4,912,203 to Kluger et al., which teaches coloring agents having theformula:

wherein R₁, R₂ and R₃ are selected from halogen, carboxylic acid,alkanoyl, aryloyl, carbocyclic forming polymethylene chains, alkyl,aryl, cyano, thioalkyl, dithioalkyl, thioaryl, dithioaryl, thiocyano,carboxyalkyl, carboxyaryl, amidoalkyl, amidodialkyl, amidoaryl,amidodiaryl, oxyalkyl, thioamidoalkyl, thioamidodialkyl, or hydrogenwhen an adjacent group is isobutyryl; R₄, R₅, R₆ and R₇ are selectedfrom hydrogen, alkyl, oxyalkyl, oxyaryl, sulfonamidoalkyl,sulfonamidoaryl, amidoalkyl, amidodialkyl, amidoaryl, amidodiaryl,halogen, thioalkyl and thioaryl; and R₈ and R₉ are polyalkylene oxideshaving an average molecular weight of from about 44 to about 2500selected from polyethylene oxide, polypropylene oxide, polybutyleneoxide and copolymers of polyethylene oxide, polypropylene oxide andpolybutylene oxide.

Note also that ethylene oxide, propylene oxide and butylenes oxide areshown below by their typical designation of “EO,” “PO” and “BO,”respectively. The average length and composition of the polymericcomponents of the whitening agents in Tables 1A and 1B is obtained fromthe formula: (Block 1+Block 2+Block 3)/(number of chains). For example,the average structure for Violet thiophene_(—)5EO consists of athiophene chromophore with 2 chains on the nitrogen, one equal to 3EOand one equal to 2EO. Chain caps are present on all polymericcomponents.

TABLE 1A Identification of Inventive Whitening Agents Sample # ofExample No. Identification Block 1 Block 2 Block 3 Chains Chain capsExample 1 Violet 3 EO — — 2 OH thiophene_3EO Example 2 Violet 5 EO — — 2OH thiophene_5EO Example 3 Violet 10 EO  — — 2 OH thiophene_10EO Example4 Violet 2 EO 6 PO — 2 OH thiophene_2EO_6PO Example 5 Violet 5 EO 5 PO —2 OH thiophene_5EO_5PO Example 6 Violet 2 EO 13 PO  — 2 OHthiophene_2EO_13PO Example 7 Violet 2 EO 14 PO  8 EO 2 OHthiophene_2EO_14PO_8EO Example 8 Violet 10 EO  14 PO  — 2 OHthiophene_10EO_14PO Example 9 Violet 10 EO  8 BO — 2 OHthiophene_10EO_8BO Example 10 Violet 5 EO — — 2 COCH₂CHRCOOHthiophene_5EO_COCH₂CHRCOOH_RC₈H₁₇ R═C₈H₁₇ Example 11 Violet 5EO — — 2COCH₃ thiophene_5EO_COCH₃ Example 12 Violet (CH₂CHOHCH₂OH)₂ — — 2 OHthiophene_glycidol Example 13 Violet (CH₂CHOHCH₂O—)₂ 5 EO — 2 OHthiophene_glycidol_5EO ^((a)) Example 14 Violet [CH₂CHOHCH₂N⁺(CH₃)₃]₂ —— 2 —N⁺(CH₃)₃ thiophene_QUAT Example 15 Triphenylmethane_10EO (10 EO)₂ —— 4 OH Example 16 Triphenylmethane_30EO (30 EO)₂ — — 4 OH Example 17Triphenylmethane_2EO_2PO (2EO)₂ (2 PO)₂ — 4 OH ^((a)) EO groups areadded to the terminal OH group.

TABLE 1B Identification of Inventive Whitening Agents Example Sample #of Chain No. Identification Alky/aryl Block 1 Block 2 Block 3 Chainscaps Example Thiophene Violet CH₂CH₃ (CH₂CHOHCH₂OH) — — 2 OH 18 N-Ethyl,N-glycidyl Example Thiophene Violet CH₂CH₃ 5EO — — 1 OH 19 N-Ethyl, 5EOExample Violet thiophene — (CH₂CH(O—)CH₂OC(CH₃)₃)₂ 5EO — 2 OH 20N,N-Bisglycidyl t-butyl ether 5 EO Example Violet thiophene —(CH₂CH(O—)CH₂OC_(9,13)H_(18,26)CH₃)₂ 5EO — 2 OH 21 N,N-Bisglycidyldo/tetradecyl ether 5 ethoxylate Example Violet thiophene —(CH₂CH(O—)CH₂OCH(C₂H₆))₂ — — 2 OH 22 N,N-Bisglycidyl isopropyl ether 5ethoxylate Example Violet thiophene — (CH₂CH(O—)CH₂OCH₂CH₂CH₂CH₃)₂ — — 2OH 23 N,N-Bisglycidyl n-butyl ether 5 ethoxylated Example Violetthiophene CH₂C₆H₅ 5EO — — 1 OH 24 N-Benzyl, 5-Ethoxylate Example Violetthiophene CH₂CH₃ CH₂CH(O—)CH₂OC(CH₃)₃ 5EO — 1 OH 25 N-Ethyl,N-t-butyl-glycidyl ether 5 ethoxylate (a) EO groups are added to theterminal OH group.

B. Calculation of Whiteness: CIELab b* and Ganz and CIE Whiteness Index

Whiteness Index (“WI”) is a qualifying assessment of color that iscalculated by a formula which includes three components of colormeasurement—hue, saturation, and lightness—which is then indexed to astandard white value. Several whiteness formulas can be used to measurewhiteness on cellulose based substrates. Two common formulas are theGanz Whiteness Index and CIE Whiteness. Ganz Whiteness Index isexpressed by the formula: WI=(D*Y) +(P*x)+(Q*y)+C, where Y, x and y arecolorimetric values and D, P, Q and C are formula parameters. CIEWhiteness is expressed by the formula: WI=Y−(800*×)−(1700*y)+813.7,where Y, x and y are colorimetric values. Further information isavailable in the publication of Rolf Griesser, Ciba-Geigy Ltd,“Whiteness and Tint”, June 1993.

The surface color of an article may be quantified using a series ofmeasurements—L*, a*, and b*—generated by measuring the samples using aspectrophotometer. The equipment used for this test is a Gretag MacbethColor Eye 7000A spectrophotometer. The software program used is “Colorimatch.” “L” is a measure of the amount of white or black in a sample;higher “L” values indicate a lighter colored sample. A measure of theamount of red or green in a sample is determined by “a*” values. Ameasure of the amount of blue or yellow in a sample is determined by“b*” values; lower (more negative) b* values indicate more blue on asample.

Yet another measurement of the relative color of a substrate is DE CMC.DE CMC is a measure of the overall color difference for all uniformcolor spaces, where DE CMC represents the magnitude of differencebetween a color and a reference (in this case, a pure white standard).The higher the DE CMC value, the more pronounced the difference incolor. In other words, smaller DE CMC values represent colors that arecloser to white. The Gretag Macbeth Color Eye 7000A Spectrophotometercalculates DE CMC values based on wavelength and reflectance data foreach sample.

C. Calculation of Molecular Properties

The average structure of each inventive whitening agent is drawn withMaterial Studio molecular modeling software (available from Accelrys,Inc.). Each structure's geometry is optimized by minimizing its energywith the Forcite module using the semi-empirical Universal forcefieldand the Qeq charge assignment system. The N═N bond of the diazocolorants are calculated at ˜1.270-1.275 Angstroms compared to theaverage N═N bond distance of 1.25 Angstroms.

These values are slightly shorter that those reported by Liu Jun-na etal., i.e., ˜1.3 angstroms, which are calculated for diphenyl diazo dyeswith Gaussian 98 software package and the B3LYP/6-311G method (LiuJun-na, Chen Zhi-rong, and Yuan Shen-feng, Journal of ZhejiangUniversity Science, 6B(6), 2005, pp. 584-589).

After the geometry optimization of all structures, a variety ofdescriptors are calculated. Descriptors can be categorized in thefollowing categories: 1. Structural, 2. Functional, 3. Energetic, 4.Topological, 5. Spatial, and 6. Thermodynamic.

All descriptors are calculated with the QSAR module of Material Studiosoftware, except for the total number of EO groups and PO groups on thechromophore, the Hansen solubility parameter (Solubility_parameter), andthe Hydrophile-Lipophile Balance number (MW_HLB). The latter twoparameters are calculated with ChemSW's Molecular Modeling Pro software.Descriptors are screened as potential predictors of affinity of thewhitening agent to the cellulosic substrate. Table 2 summarizes some ofthe test parameters that are used to characterize the whitening agentsof the present invention.

TABLE 2 Summary of Test Parameters Descriptor Symbol Test NameDefinition Hansen Solubility Hansen total (Hildebrand) δ² = δ²_(dispersion) + δ² _(polar) + δ² _(H-bonding) parameter, δ solubilitysum of solubility components for dispersion, polarity, and hydrogenbonding forces, respectively FPSA1 Fractional Positive Sum of thesolvent-accessible surface area of (Jurs descriptor) Surface Area allpositively-charged atoms divided by total molecular solvent-accessiblesurface area RPSA Relative Polar Surface Total polar surface areadivided by total (Jurs descriptor) Area molecular solvent-accessiblesurface area Radius of Gyration Parameter characterizing (Σm_(i) r_(i)²/Σm_(i))^(0.5), where m_(i) = mass of element the size of any shape i,r_(i) = distance of element from center of mass Dipole Moment Magnitudeof dipole Σq_(i) r_(i), where q_(i) = partial atomic charge, r_(i) =Magnitude moment from spatial distance descriptor set Polarizability Sumof atomic relative tendency of the electron cloud of a polarizabilitiesmolecule to be distorted from its normal shape by the presence of anearby ion or dipole

Test Results Test 1: Whiteness Test as Determined by CIELab b* Valuesand the Ganz Whiteness Index

Examples 1 through 17 are tested for whiteness to determine CIELab b*values and Ganz Whiteness Index (“Ganz WI”) values. Test results areprovided in Table 3. Lower (more negative) CIELab b* values and higherpositive Ganz WI values indicate that more blueing, or whitening effect,is exhibited by the treated cellulose particles.

TABLE 3 Test Results For Whiteness as Determined by CIELab b* Values andthe Ganz Whiteness Index CIELab b* Color Ganz Whiteness Value IndexValue Sample Post Rinse 1 Post Rinse 1 Control 2.66 54.34 Example 1−7.57 144.11 Example 2 −9.28 162.21 Example 3 −5.34 118.09 Example 4−6.58 135.30 Example 5 −4.12 107.80 Example 6 −3.49 102.93 Example 7−4.57 113.82 Example 8 −3.19 101.29 Example 9 −3.58 102.75 Example 10−5.76 127.03 Example 11 −4.48 112.85 Example 12 −9.37 162.00 Example 13−5.94 126.34 Example 14 −5.36 119.92 Example 15 −5.46 125.44 Example 16−3.69 107.50 Example 17 −6.51 135.99

The test results indicate that Example 2, which contained 5 ethyleneoxide repeating units, and Example 12, which contained a glycidol unit,performed the best under these test conditions. The data reveals arelatively linear correlation between CIELab b* color values and theGanz WI values. A linear regression fit for all of the data points has aregression value of R²=0.988.

Test 2: Measurement of CIELab b* Values and the Dispersion ComponentValues of Hansen Solubility Parameter

Examples 1 through 17 are tested to determine CIELab b* values and thedispersion component values of the Hansen Solubility Parameter. Notethat Examples 1 through 14 contain a violet thiophene chromophore, whileExamples 15 through 17 contain triphenylmethane colorants. Examples 18through 25 are tested to determine the dispersion component value of theHansen Solubility Parameter only.

Test results are provided in Table 4. Larger negative CIELab b* valuesindicate that more blueing, or whitening effect, is exhibited by thetreated cellulose particles. “N/A” indicates that data are notavailable.

TABLE 4 Measured CIELab b* Values and Dispersion Component Values ofHansen Solubility Parameter Dispersion Component Value of Hansen CIELabb* Solubility Parameter Color Value (MPa^(0.5)) Sample Post Rinse 1 PostRinse 1 Control  2.66 25.4 Example 1 −7.57 14.9 Example 2 −9.28 14.8Example 3 −5.34 16.6 Example 4 −6.58 17.9 Example 5 −4.12 18.4 Example 6−3.49 18.5 Example 7 −4.57 18.2 Example 8 −3.19 19.1 Example 9 −3.5818.6 Example 10 −5.76 18.5 Example 11 −4.48 19.6 Example 12 −9.37 14.1Example 13 −5.94 12.7 Example 14 −5.36 16.8 Example 15 −5.46 16.8Example 16 −3.69 19.5 Example 17 −6.51 18.5 Example 18 N/A 16.3 Example19 N/A 16.7 Example 20 N/A 15.8 Example 21 N/A 16.6 Example 22 N/A 16.0Example 23 N/A 16.2 Example 24 N/A 17.0 Example 25 N/A 16.4

The test results reveal a relatively linear correlation between theblueing parameter, CIELab b*, and the dispersion component value of theHansen Solubility Parameter. The color value b* decreases (i.e. blueingperformance increases) linearly as δ_(d) decreases.

A linear regression fit for all of the data points and has a regressionvalue of R²=0.763. The regression line has the following equation:

b_blueing=0.9704*δ_(d)−22.468   (2)

Test 3: Prediction of CIELab b* Values Based on the Dispersion ComponentValues of Hansen Solubility Parameter

Examples 1-10 and 15-17 are first used to train a model based on thedispersion component value of the Hansen Solubility Parameter. TheCIELab b* value is calculated for these Examples using Equation 3, asshown below, which utilizes the dispersion component value obtainedafter 1 rinse cycle:

b_blueing=1.0014*δ_(d)−23.02   (3)

This equation is very similar to Equation 2, which is derived using allof the Examples. The model represented by Equation 3 is validated withtest compounds in Examples 11-14. Equation 3 is used to generatepredictions for the CIELab b* value of molecules in Examples 11-14 (testmolecules) before these molecules are synthesized and tested forwhitening efficiency. The predicted CIELab b* values obtained fromEquation 3 are compared to the measured values previously obtained fromthe Gretag Macbeth Color Eye 7000A spectrophotometer. The percentdifference between measured b* color values and predicted b* colorvalues is also determined.

Dispersion component values and predicted CIELab b* values are alsodetermined for Comparative Examples 1 and 2. Comparative Example 1 is ablue polymeric anthraquinone dye disclosed in Example III of U.S. Pat.No. 4,127,243 to Farmer. Comparative Example 2 is Basic Violet 3, asdisclosed in Table 2 of US Patent Application Publication No.2005/0288206 to Sadlowski et al.

Test results are provided in Table 5 and FIG. 1. “N/A” indicates thatdata are not available.

TABLE 5 Predicted CIELab b* Values Based on Dispersion Component Valuesof Hansen Solubility Parameter After Post Rinse 1 Dispersion DifferenceComponent Between Value of Predicted Measured Predicted and HansenSolubility CIELab CIELab Measured Parameter b* b* CIELab Example No.(MPa^(0.5)) Value Value b* Values (%) Control 25.4 N/A  2.66 N/A Example1 14.9 −8.1 −7.57 6.6 Example 2 14.8 −8.2 −9.28 −13.2 Example 3 16.6−6.4 −5.34 17.0 Example 4 17.9 −5.1 −6.58 −29.9 Example 5 18.4 −4.6−4.12 10.6 Example 6 18.5 −4.5 −3.49 22.2 Example 7 18.2 −4.8 −4.57 5.0Example 8 19.1 −3.8 −3.19 16.4 Example 9 18.6 −4.4 −3.58 19.3 Example 1018.5 −4.5 −5.76 −27.6 Example 11 19.6 −4.3 −4.48 −3.8 Example 12 14.1−8.9 −9.37 −4.9 Example 13 12.7 −8.7 −8.25 5.2 Example 14 16.8 −6.2−5.32 14.4 Example 15 16.8 −6.2 −5.46 12.3 Example 16 19.5 −3.5 −3.69−4.7 Example 17 18.5 −4.4 −6.51 −46.4 Comparative 21.3 −1.7 N/A N/AExample 1 Comparative 19.5 −3.5 N/A N/A Example 2

Example 11 (Violet thiophene_(—)5EO_COCH3) and Example 12 (Violetthiophene_glycidol) are synthesized and tested to verify that the modelcan explain the effects of the functionality of the polymeric chain endcaps. Example 12 has four hydroxyl groups, while whitening agents withEO or PO end groups have only 2 hydroxyl groups. Example 11 has roughlythe same size as Example 12, but the acetate caps are less polar thanthe OH groups.

FIG. 1 provides a graphical representation of the data. The phrase“violet thiophene” is shown as “violet” and “triphenylmethane” is shownas “TPM” on FIG. 1. The data points represent the measured CIELab b*color values. The solid line represents Equation 3, which is thepredicted data. The linear correlation between color value b* and δ_(d)suggests that the smaller the molecule the stronger the deposition onthe cellulose powder. The size of the whitening agent compound mayinfluence its ability to access and diffuse into the pores of thecellulose powder. In addition, whitening agents having a more polar capon the chains of the molecule, or those whitening agents having agreater number of polar end groups, exhibited greater blueing efficacy.The calculations also show that triphenylmethane-containing whiteningagents are preferred whitening agents.

Exemplary Detergent Formulations Formulations 1a-1l: Liquid DetergentFormulations

Tables 6A and 6B provide examples of liquid detergent formulations whichinclude at least one whitening agent of the present invention. Theformulations are shown in Table 6A as Formulations 1a through 1f and inTable 6B as Formulations 1g through 1l.

TABLE 6A Liquid Detergent Formulations Comprising the InventiveWhitening Agent 1a 1b 1c 1d 1e 1f⁵ Ingredient wt % wt % wt % wt % wt %wt % sodium alkyl ether sulfate 14.4%  14.4%  9.2% 5.4% linearalkylbenzene sulfonic 4.4% 4.4% 12.2%  5.7% 1.3% 22.0%  acid alkylethoxylate 2.2% 2.2% 8.8% 8.1% 3.4% 18.0%  amine oxide 0.7% 0.7% 1.5%citric acid 2.0% 2.0% 3.4% 1.9% 1.0% 1.6% fatty acid 3.0% 3.0% 8.3%16.0%  protease 1.0% 1.0% 0.7% 1.0% 2.5% amylase 0.2% 0.2% 0.2% 0.3%lipase 0.2% borax 1.5% 1.5% 2.4% 2.9% calcium and sodium formate 0.2%0.2% formic acid 1.1% amine ethoxylate polymers 1.8% 1.8% 2.1% 3.2%sodium polyacrylate 0.2% sodium polyacrylate 0.6% copolymer DTPA¹ 0.1%0.1% 0.9% DTPMP² 0.3% EDTA³ 0.1% fluorescent whitening agent 0.15% 0.15%  0.2% 0.12%  0.12%  0.2% ethanol 2.5% 2.5% 1.4% 1.5% propanediol6.6% 6.6% 4.9% 4.0% 15.7%  sorbitol 4.0% ethanolamine 1.5% 1.5% 0.8%0.1% 11.0%  sodium hydroxide 3.0% 3.0% 4.9% 1.9% 1.0% sodium cumenesulfonate 2.0% silicone suds suppressor 0.01%  perfume 0.3% 0.3% 0.7%0.3% 0.4% 0.6% Example 15 table 1 0.001%  0.0005%   Example 2 table 10.013%  0.005%  0.003%  0.001%  water balance balance balance balancebalance balance 100.0%  100.0%  100.0%  100.0%  100.0%  100.0% 

TABLE 6B Liquid Detergent Formulations Comprising the InventiveWhitening Agent 1g 1h 1i 1j 1k 1l⁶ Ingredient wt % wt % wt % wt % wt %wt % sodium alkyl ether sulfate 14.4%  14.4%  9.2% 5.4% linearalkylbenzene sulfonic 4.4% 4.4% 12.2%  5.7% 1.3% 22.0%  acid alkylethoxylate 2.2% 2.2% 8.8% 8.1% 3.4% 18.0%  amine oxide 0.7% 0.7% 1.5%citric acid 2.0% 2.0% 3.4% 1.9% 1.0% 1.6% fatty acid 3.0% 3.0% 8.3%16.0%  protease 1.0% 1.0% 0.7% 1.0% 1.7% amylase 0.2% 0.2% 0.2% 0.6%lipase 0.2% 0.2% borax 1.5% 1.5% 2.4% 2.9% calcium and sodium formate0.2% 0.2% formic acid 1.1% amine ethoxylate polymers 1.8% 1.8% 2.1% 3.2%sodium polyacrylate 0.2% sodium polyacrylate 0.6% copolymer DTPA¹ 0.1%0.1% 0.9% DTPMP² 0.3% EDTA³ 0.1% fluorescent whitening agent 0.15% 0.15%  0.2% 0.12%  0.12%  0.2% ethanol 2.5% 2.5% 1.4% 1.5% propanediol6.6% 6.6% 4.9% 4.0% 15.7%  sorbitol 4.0% ethanolamine 1.5% 1.5% 0.8%0.1% 11.0%  sodium hydroxide 3.0% 3.0% 4.9% 1.9% 1.0% sodium cumenesulfonate 2.0% silicone suds suppressor 0.01%  perfume 0.3% 0.3% 0.7%0.3% 0.4% 0.6% Example 15 table 1 0.01%  0.005%  Example 2 table 10.01%  0.02% 0.003%  0.012%  opacifier⁹ 0.5% water balance balancebalance balance balance balance 100.0%  100.0%  100.0%  100.0%  100.0% 100.0%  Footnotes for Formulations 1a-l: ¹diethylenetriaminepentaaceticacid, sodium salt ²diethylenetriaminepentakismethylenephosphonic acid,sodium salt ³ethylenediaminetetraacetic acid, sodium salt ⁴a non-tintingdyes used to adjust formula color ⁵compact formula, packaged as aunitized dose in polyvinyl alcohol film ⁶alkoxylated anthraquinonecolorant with hueing efficiency >10 and wash removability 30-85%⁷alkoxylated thiophene colorant with hueing efficiency >10 and washremovability 30-85% ⁸alkoxylated triphenylmethane colorant with hueingefficiency >10 and wash removability 30-85% ⁹Acusol OP301

Formulations 2a-2e: Granular Detergent Formulations

Table 7 provides examples of granular detergent formulations whichinclude at least one whitening agent of the present invention. Theformulations are shown in Table 7 as Formulations 2a through 2e.

TABLE 7 Granular Detergent Formulations Comprising the InventiveWhitening Agent Ingredient 2a 2b 2c 2d 2e wt % wt % wt % wt % wt % Nalinear alkylbenzene  3.4%  3.3%  11.0%  3.4%  3.3% sulfonate Naalkylsulfate  4.0%  4.1%  4.0%  4.1% Na alkyl sulfate  9.4%  9.6%  9.4% 9.6% (branched) alkyl ethoxylate  3.5% type A zeolite  37.4%  35.4% 26.8%  37.4%  35.4% sodium carbonate  22.3%  22.5%  35.9%  22.3%  22.5%sodium sulfate  1.0%  18.8%  1.0% sodium silicate  2.2% protease  0.1% 0.2%  0.1%  0.2% sodium polyacrylate  1.0%  1.2%  0.7%  1.0%  1.2%carboxymethylcellulose  0.1% PEG 600  0.5%  0.5% PEG 4000  2.2%  2.2%DTPA  0.7%  0.6%  0.7%  0.6% fluorescent whitening  0.1%  0.1%  0.1% 0.1%  0.1% agent sodium percarbonate  5.0%  5.0% sodium nonanoyloxy- 5.3%  5.3% benzenesulfonate silicone suds suppressor  0.02%  0.02% 0.02%  0.02% perfume  0.3%  0.3%  0.2%  0.3%  0.3% Example 15 table 10.004%  0.02% Example 2 table 1 0.006% 0.002% 0.004% water andmiscellaneous bal- bal- bal- bal- bal- ance ance ance ance ance 100.0%100.0% 100.0% 100.0% 100.0%

Exemplary Fabric Care Compositions Formulations 3a-3d: Liquid FabricCare Compositions

Table 8 provides examples of liquid fabric care compositions whichinclude at least one whitening agent of the present invention. Thecompositions are shown in Table 8 as Formulations 3a through 3d.

TABLE 8 Liquid Fabric Care Compositions Comprising the InventiveWhitening Agent Ingredients 3a 3b 3c 3d Fabric Softening Active ^(a)13.70% 13.70% 13.70% 13.70% Ethanol  2.14%  2.14%  2.14%  2.14% CationicStarch ^(b)  2.17%  2.17%  2.17%  2.17% Perfume  1.45%  1.45%  1.45% 1.45% Phase Stabilizing Polymer ^(c)  0.21%  0.21%  0.21%  0.21%Calcium Chloride 0.147% 0.147% 0.147% 0.147% DTPA ^(d) 0.007% 0.007%0.007% 0.007% Preservative ^(e)  5 ppm  5 ppm  5 ppm  5 ppm Antifoam^(f) 0.015% 0.015% 0.015% 0.015% Example 1 of Table 1 30 ppm 15 ppmExample 2 of Table 1 30 ppm Example 3 of Table 1 30 ppm 15 ppm TinopalCBS-X ^(g) 0.2 0.2 0.2 0.2 Ethoquad C/25 ^(h) 0.26 0.26 0.26 0.26Ammonium Chloride  0.1%  0.1%  0.1%  0.1% Hydrochloric Acid 0.012%0.012% 0.012% 0.012% Deionized Water Balance Balance Balance Balance^(a) N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride. ^(b)Cationic starch based on common maize starch or potato starch,containing 25% to 95% amylose and a degree of substitution of from 0.02to 0.09, and having a viscosity measured as Water Fluidity having avalue from 50 to 84. ^(c) Copolymer of ethylene oxide and terephthalatehaving the formula described in U.S. Pat. No. 5,574,179 at col. 15,lines 1-5, wherein each X is methyl, each n is 40, u is 4, each R¹ isessentially 1,4-phenylene moieties, each R² is essentially ethylene,1,2-propylene moieties, or mixtures thereof. ^(d)Diethylenetriaminepentaacetic acid. ^(e) KATHON ® CG available from Rohmand Haas Co. ^(f) Silicone antifoam agent available from Dow CorningCorp. under the trade name DC2310. ^(g) Disodium4,4′-bis-(2-sulfostyryl) biphenyl, available from Ciba SpecialtyChemicals. ^(h) Cocomethyl ethoxylated [15] ammonium chloride, availablefrom Akzo Nobel.

Accordingly, the present invention provides a whitening agent forcellulosic substrates comprising at least one chromophore component thatcomprises a thiophene or triphenylmethane colorant and at least onepolymeric component; wherein the whitening agent possesses a dispersioncomponent value of the Hansen Solubility Parameter of less than or equalto about 17 MPa^(0.5). A laundry detergent containing such a whiteningagent is also contemplated herein.

The whitening agent of the present invention includes a whitening agentfor cellulosic substrates comprising at least one chromophore componentthat comprises a thiophene colorant and at least one polymeric componentwherein the whitening agent is characterized by the following structure:

Wherein R₁ and R₂ can independently be selected from:

-   -   -   a) [CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H]            -   wherein R′ is selected from the group consisting of H,                CH₃, CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein                R″ is selected from the group consisting of H,                CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein x+y≦5;                wherein y≧1; and wherein z=0 to 5;

    -   b) R₁=alkyl, aryl or aryl alkyl and        R₂═[CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H]        wherein R′ is selected from the group consisting of H, CH₃,        CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is selected        from the group consisting of H, CH₂O(CH₂CH₂O)_(z)H, and mixtures        thereof; wherein x+y≦10; wherein y≧1; and        -   wherein z=0 to 5;

    -   c) R₁═[CH₂CH₂(OR₃)CH₂OR₄] and R₂═[CH₂CH₂(OR₃)CH₂O R₄]        -   wherein R₃ is selected from the group consisting of H,            (CH₂CH₂O)_(z)H, and mixtures thereof; and wherein z=0 to 10;        -   wherein R₄ is selected from the group consisting of            (C₁-C₁₆)alkyl, aryl groups, and mixtures thereof; and

    -   d) wherein R₁ and R₂ can independently be selected from the        amino addition product of styrene oxide, glycidyl methyl ether,        isobutyl glycidyl ether, isopropylglycidyl ether, t-butyl        glycidyl ether, 2-ethylhexylgycidyl ether, and glycidylhexadecyl        ether, followed by the addition of from 1 to 10 alkylene oxide        units.

The whitening agent of the present invention also includes a whiteningagent for cellulosic substrates comprising at least one chromophorecomponent that comprises a thiophene colorant and at least one polymericcomponent wherein the whitening agent is characterized by the followingstructure:

Wherein R₁ and R₂ are independently selected from:

-   -   a) [CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H]        -   wherein R′ is selected from the group consisting of H, CH₃,            CH₂O(CH₂CH₂O)_(z)H; wherein R″ is selected from the group            consisting of H, CH₂O(CH₂CH₂O)_(z)H; wherein x+y≦5;        -   wherein y≧1; and wherein z=0 to 5;    -   b) R₁=alkyl, aryl or aryl alkyl and        R₂═[CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H]        -   wherein R′ is selected from the group consisting of H, CH₃,            CH₂O(CH₂CH₂O)_(z)H; wherein R″ is selected from the group            consisting of H, CH₂O(CH₂CH₂O)_(z)H; wherein x+y≦10;        -   wherein y≧1; and wherein z=0 to 5;    -   c) R₁═[CH₂CH₂(OR₃)CH₂OR₄] and R₂═[CH₂CH₂(OR₃)CH₂OR₄]        -   wherein R₃ is selected from the group consisting of H,            (CH₂CH₂O)_(z)H; and wherein z=0 to 10;        -   wherein R₄ is selected from the group consisting of            (C₁-C₁₆)alkyl, aryl groups; and    -   d) wherein R₁ and R₂ can independently be selected from the        amino addition product of styrene oxide, glycidyl methyl ether,        isobutyl glycidyl ether, isopropylglycidyl ether, t-butyl        glycidyl ether, 2-ethylhexylgycidyl ether, and glycidylhexadecyl        ether, followed by the addition of from 1 to 10 alkylene oxide        units; and

Wherein R₅, R₆, R₇ and R₈ are independently selected from the groupconsisting of hydrogen, alkyl, oxyalkyl, oxyaryl, sulfonaidoalkyl,sulfonamidoaryl, amidoalkyl, amidodialkyl, amidoaryl, amidodiaryl,halogen, thioalkyl and thioaryl.

A potentially preferred whitening agent of the present inventionincludes a whitening agent for cellulosic substrates comprising at leastone chromophore component that comprises a thiophene colorant and atleast one polymeric component wherein the whitening agent ischaracterized by the following structure:

-   -   wherein R′ is selected from the group consisting of H, CH₃,        CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is selected        from the group consisting of H, CH₂O(CH₂CH₂O)_(z)H, and mixtures        thereof; wherein x+y≦5; wherein y≧1; and wherein z=0 to 5.

Additionally, the present invention provides a whitening agentcharacterized by a CIELab b* color value (“b”) and a dispersioncomponent value of the Hansen Solubility Parameter (“δ_(d)”), wherein“b” and “δ_(d)” exhibit an approximately linear correlation with eachother according to the following equation: b=1.00(δ_(d))−23. A laundrydetergent containing such a whitening agent is also contemplated herein.

Thus, it is believed to be an advantage of the present invention toemploy the predictive model to aid in the selection ofchromophore-containing compounds ideally suited as whitening agents.Test results provided herein tend to indicate that deposition of thewhitening agent on the cellulose powder may be controlled, at least inpart, by the size of the whitening agent compound and by its chain capfunctionality. Test results also suggest that larger molecules may betoo bulky to diffuse into the pores of the cellulose powder which maydecrease the whitening effect after multiple washing and/or rinsingcycles.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A whitening agent for cellulosic substrates comprising: (a) at leastone chromophore component that comprises a thiophene or triphenylmethanecolorant, wherein the chromophore component exhibits an absorbancespectrum in water of from 520 nanometers to 640 nanometers, and (b) atleast one polymeric component; wherein the whitening agent possesses adispersion component value of the Hansen Solubility Parameter of lessthan or equal to about 17 MPa^(0.5).
 2. The whitening agent of claim 1,wherein the whitening agent possesses a dispersion component value ofthe Hansen Solubility Parameter from about 12 to about 17 MPa^(0.5). 3.The whitening agent of claim 1, wherein the whitening agent comprises apolyoxyalkylene chain having from 2 to about 20 repeating units.
 4. Thewhitening agent of claim 1, wherein the whitening agent comprises atleast two hydroxyl groups.
 5. The whitening agent of claim 4, whereinthe hydroxyl groups are primary hydroxyl moieties.
 6. The whiteningagent of claim 1, wherein the whitening agent comprises an alkoxylatedtriphenylmethane polymeric colorant.
 7. The whitening agent of claim 1,wherein the whitening agent comprises an alkoxylated thiophene polymericcolorant.
 8. The whitening agent of claim 1, wherein the whiteningagent's chromophore exhibits an emission spectrum in water of from about400 nanometers to about 480 nanometers.